Removal of vanadium and/or sodium from petroleum and petroleum products with alumina and iron oxide



limited States Patent REMOVAL OF VANADIUM AND/0R SODIUM FROM PETROLEUM AND PETROLEUM PIODUCTS WITH ALUMINA AND IRON 0 IDE Frederick William Bertram Porter and Roy Purdy Northcott, Sunbury-on-Thames, England, assignors to The British Petroleum Company Limited, a British jointstock corporation No Drawing. Application June 16, 1953, Serial No. 362,144

In co-pending U. S. application Serial No. 263,956, filed December 28, 1951, there is described a process in which vanadium and/or sodium are/is removed from petroleum or petroleum products by contact with bauxite in the presence or absence of hydrogen and under conditions of temperature and pressure such that the vanadium and/or sodium are/is deposited on or incorporated with the baumte. It was later discovered that the degree of vanadium and/ or sodium removal under any given set of operating conditions tended to vary with bauxites of difierent origins.

It has now been found that vanadium and/or sodium in petroleum or petroleum products can be removed by treatment with iron oxide on alumina.

According to the invention therefore, a process for removing vanadium and/ or sodium from crude petroleum or a petroleum product comprises contacting the crude petroleum or petroleum product with a contact material consisting essentially of iron oxide and alumina, in the presence of hydrogen and under conditions of temperature and pressure such that vanadium and/or sodium are/ is deposited on the contact material.

The contact material preferably contains from 515% by weight of ferric oxide the remainder consisting essentially of alumina.

The preferred ranges of operating conditions for the process are as follows:

Space velocity 0.5 to 2.0 v./v./hr. Temperature 750 to 800 F.

Pressure 500 to 1500 p. s. i. g. a. Hydrogen recycle rate 1000 to 10,000 S. C. F./B.

The process of the invention is particularly adaptable as a pre-treatment process for crude petroleum or petroleum products which are to be passed to a catalytic hydrogenation process for the removal of organically combined sulphur. For example, it has been found that in the hydrofining of crude petroleum and petroleum residues using a catalyst consisting of cobalt and molybdenum oxides supported on alumina, substantial proportions of vanadium and sodium are removed by and deposited on the catalyst and this deposition causes a steady decline in catalyst activity with hours on stream which is not wholly recovered on regeneration in the conventional manner. This invention, therefore, also includes a continuous process wherein a petroleum feedstock containing vanadium and/or sodium is first treated with iron oxide on alumina, as above described, and is then passed to a hydrogenation zone for the removal of organically combined sulphur.

An example of the application of the invention to the treatment of a petroleum residue will now be given.

EXAMPLE Sodium and vanadium removal from Kuwait 53% volume residue.

Conditions employed Feedstock Kuwait 53% vol. residue. Space velocity 1.0 v./v./hr. Temperature. 780 F. Pressure 1000 p. s. i. g. a. Hydrogen recycle rate 4000 S. C. F./B. Direction of flow Upward. Duration of test 50 hours.

Results obtained IRON OXIDE 0N ALUMINA [12.8% wt. ezOa] Product Feedstock (bulk over 50 hrs.)

Vanadium, p. p. m 41 21 Sodium, p. p. m 39 28 Sulphur, percent wt 3. 89 3. 42 Specific Gravity, F./60 F 0.958 0. 943

We claim: A process for removing vanadium and sodium from a crude petroleum feedstock comprising contacting the petroleum feedstock with a contact material consisting essentially of alumina to which has been added 5-15 by weight of ferric oxide in the presence of hydrogen and at a temperature within the range of about 750800 F. and a pressure within the range of about 500-1500 p. s. i. g. a. such that vanadium and sodium are deposited on the contact material.

References Cited in the file of this patent UNITED STATES PATENTS 1,882,000 Cross Oct. 11, 1932 2,116,061 Dorrer May 3, 1938 2,227,089 Hopper Dec. 31, 1940 2,383,972 Jones Sept. 4, 1945 2,411,958 Dietrich et a1. Dec. 3, 1946 2,507,523 Houdry May 16, 1950 2,687,985 Porter et a1. Aug. 31, 1954 

